[(Pyridine-2,6-dicarboxyl­ato)copper(II)]-μ-(pyridine-2,6-dicarboxyl­ato)-[bis­(ethyl­enediamine)­copper(II)]-μ-(pyridine-2,6-dicarboxyl­ato)-[(pyridine-2,6-dicarboxyl­ato)copper(II)] ethyl­enediamine monosolvate tetra­hydrate

Shokooh Saljooghi, A.; Amiri Rudbari, H.; Nicolò, F.; Zahmati, M.; Delavar Mendi, F.

doi:10.1107/S1600536812022039

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m830-m831

doi:10.1107/S1600536812022039

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[(Pyridine-2,6-dicarboxylato)copper(II)]-μ-(pyridine-2,6-dicarboxylato)-[bis(ethylenediamine)copper(II)]-μ-(pyridine-2,6-dicarboxylato)-[(pyridine-2,6-dicarboxylato)copper(II)] ethylenediamine monosolvate tetrahydrate

Amir Shokooh Saljooghi,^a ^* Hadi Amiri Rudbari,^b Francesco Nicolò,^b Maliheh Zahmati ^a and Fatemeh Delavar Mendi ^a

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran, and ^bDipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone, 31 Contrada Papardo, 98166 Messina, Italy
^*Correspondence e-mail: amir.saljooghi@yahoo.com

(Received 28 April 2012; accepted 15 May 2012; online 26 May 2012)

The title compound, [Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂]·C₂H₈N₂·4H₂O, was obtained by the reaction of copper(II) acetate dihydrate with pyridine-2,6-dicarboxylic acid (H₂dipic) and ethylenediamine (en) in an aqueous solution. All of the Cu^II atoms in the trinuclear centrosymmetric title complex are six-coordinated in a distorted octahedral geometry with N₂O₄ and N₄O₂ environments for the outer and central Cu^II atoms, respectively. Various interactions, including numerous O—H⋯O and C—H⋯O hydrogen bonds and C—O⋯π stacking of the pyridine and carboxylate groups [O⋯centroid distances = 3.669 (2) and 3.668 (2) Å] are observed in the crystal structure.

Related literature

For metal complexes formed by pyridinedicarboxylic acids, see: Aghabozorg et al. (2006 ); Burdock (1996 ); Douki et al. (2005 ); Kazuhiro et al. (1994 ); Murakami et al. (2003); Park et al. (2007 ); Xie et al. (2006 ).

Experimental

Crystal data

[Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂]·C₂H₈N₂·4H₂O
M_r = 1105.43
Monoclinic, P 2₁ /n
a = 8.152 (2) Å
b = 20.538 (5) Å
c = 12.736 (3) Å
β = 93.44 (2)°
V = 2128.5 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 293 K
0.51 × 0.28 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007) T_min = 0.583, T_max = 0.747
35349 measured reflections
9453 independent reflections
6734 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.100
S = 1.02
9453 reflections
336 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O1	0.84 (2)	2.07 (2)	2.8697 (17)	160 (2)
O10—H10B⋯O2	0.92 (2)	1.87 (2)	2.7927 (17)	176 (3)
N5—H5A⋯O9	0.89	1.93	2.808 (2)	167
O9—H9B⋯O5	0.88 (2)	2.50 (2)	3.211 (2)	139 (3)
O9—H9B⋯O6	0.88 (2)	1.96 (2)	2.793 (2)	159 (3)
N3—H3A⋯O6ⁱ	0.87 (2)	2.51 (2)	3.218 (2)	138.5 (18)
O9—H9A⋯O10ⁱⁱ	0.83 (2)	2.10 (2)	2.893 (3)	160 (3)
N5—H5B⋯O9ⁱⁱⁱ	0.89	2.59	3.106 (2)	118
N5—H5B⋯O10^iv	0.89	2.06	2.9151 (19)	160
N5—H5C⋯O4^v	0.89	1.82	2.6882 (18)	166
N4—H4A⋯O8^vi	0.843 (19)	2.482 (19)	3.2079 (19)	144.8 (17)
O10—H10A⋯O8^vii	0.88 (2)	1.82 (2)	2.6824 (17)	165 (2)
N3—H3B⋯O8^vii	0.80 (2)	2.31 (3)	3.0664 (19)	156 (2)
N3—H3B⋯O7^vii	0.80 (2)	2.43 (2)	3.1383 (17)	147 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+2, -z+1; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+2, -z+1; (vi) x-1, y, z; (vii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022039/qm2066sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022039/qm2066Isup2.hkl

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (also known as 2,6-dicarboxypyridine and as dipicolinic acid, H₂dipic) is a water-soluble, commercially available, cheap and versatile N,O-chelator possessing diverse coordination modes, with a recognized biological function in the body metabolism (Douki et al., 2005),and in a variety of processes as an enzyme inhibitor (Murakami et al., 2003), plant preservative (Kazuhiro et al., 1994), and food sanitizer (Burdock, 1996),. The complexation of transition metal ions from dipicolinic acid has been the subject of numerousreports. The reasons for this interest are the ability of the ligand so it gave stable chelates with different coordination modes (Park et al., 2007), affinity to form strong hydrogen bonds and its biological activity in human metabolism (Xie et al., 2006). A lots of dipicolinate complexes of transition metals and main groups are known and reported (Xie et al., 2006; Aghabozorg et al., 2006). Here, we report the crystal structure of the title binuclear complex, [Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂].(C₂H₈N₂).2H₂O, in which the Pyridine-2,6-dicarboxylic acid (C₇H₃NO₄) species acts as a momo and tridentate ligand. In the crystal structure, the copper atoms are in three types. All copper atoms exhibit an distorted octahedral coordination geometry. In the crystal structure, Cu (1) is coordinated by two dipicolinic acid ligands, and Cu (2) is coordinated by two ethylenediamine molecules and two uncoordinated O atoms of two dipicolinic acid groups linked to Cu (1). As shown in Fig.1, this causes that Cu (2) makes a bridge between two Cu (1) atoms. The bond distances of Cu(1)– O(1) and Cu(1)– O(3) is longer than Cu(1)–N(1), Cu(1)–N(2), Cu(1)–O(5) and Cu(1)–O(7) bond distances due to Jahn–Teller effect. Also 0.74 Å difference between Cu(2)–O and Cu(2)–N bonds, due to Jahn–Teller effect. There are extensive intermolecular O—H···O, N—H···O and weak C—H···O hydrogen bonds, which cause the stability of the crystal structure (Fig. 2).

Related literature top

For metal complexes formed by pyridinedicarboxylic acids, see: Aghabozorg et al. (2006); Burdock (1996); Douki et al. (2005); Kazuhiro et al. (1994); Murakami et al. (2003); Park et al. (2007); Xie et al. (2006).

Experimental top

To an aqueous solution of Copper(II) acetate, an aqueous solution of H₂dipic and en in 1:1:1 molar ratio was added. The final volume was 30 ml. After less than 1 h stirring, the obtained blue solution was left for 3 days. Then the blue crystals of the title compound were obtained for X-ray crystallography.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure and atom labeling scheme for title compound with displacement ellipsoids at the 50% probability level.
	Fig. 2. A packing view of the title compound. Hydrogen bonds are shown with dashed lines.

[(Pyridine-2,6-dicarboxylato)copper(II)]-µ-(pyridine-2,6-dicarboxylato)- [bis(ethylenediamine)copper(II)]-µ-(pyridine-2,6-dicarboxylato)-[(pyridine- 2,6-dicarboxylato)copper(II)] ethylenediamine monosolvate tetrahydrate top

Crystal data top

[Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂]·C₂H₈N₂·4H₂O	F(000) = 1134
M_r = 1105.43	D_x = 1.725 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8052 reflections
a = 8.152 (2) Å	θ = 2.6–32.5°
b = 20.538 (5) Å	µ = 1.58 mm⁻¹
c = 12.736 (3) Å	T = 293 K
β = 93.44 (2)°	Irregular, blue
V = 2128.5 (10) Å³	0.51 × 0.28 × 0.12 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	9453 independent reflections
Radiation source: fine-focus sealed tube	6734 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 35.2°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→13
T_min = 0.583, T_max = 0.747	k = −33→33
35349 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0528P)² + 0.1097P] where P = (F_o² + 2F_c²)/3
9453 reflections	(Δ/σ)_max = 0.003
336 parameters	Δρ_max = 0.48 e Å⁻³
5 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂]·C₂H₈N₂·4H₂O	V = 2128.5 (10) Å³
M_r = 1105.43	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.152 (2) Å	µ = 1.58 mm⁻¹
b = 20.538 (5) Å	T = 293 K
c = 12.736 (3) Å	0.51 × 0.28 × 0.12 mm
β = 93.44 (2)°

Data collection top

Bruker APEXII CCD diffractometer	9453 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	6734 reflections with I > 2σ(I)
T_min = 0.583, T_max = 0.747	R_int = 0.034
35349 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	5 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.48 e Å⁻³
9453 reflections	Δρ_min = −0.47 e Å⁻³
336 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.41369 (2)	0.734887 (8)	0.553105 (12)	0.02551 (5)
N1	0.38865 (14)	0.73453 (5)	0.39949 (8)	0.02225 (19)
O5	0.26265 (15)	0.81147 (5)	0.60629 (9)	0.0362 (2)
O3	0.58419 (15)	0.81797 (6)	0.50570 (8)	0.0368 (2)
N2	0.44168 (14)	0.72476 (5)	0.70320 (8)	0.02212 (19)
C2	0.29612 (16)	0.68844 (6)	0.35084 (10)	0.0236 (2)
C6	0.46747 (16)	0.77861 (6)	0.34388 (10)	0.0233 (2)
C9	0.36906 (16)	0.76619 (6)	0.76552 (10)	0.0229 (2)
O1	0.21166 (16)	0.65984 (5)	0.51771 (8)	0.0374 (3)
O2	0.15002 (16)	0.59160 (5)	0.38441 (9)	0.0401 (3)
C13	0.53495 (16)	0.67598 (6)	0.74101 (10)	0.0240 (2)
C10	0.38875 (18)	0.75991 (7)	0.87363 (11)	0.0302 (3)
H10	0.3384	0.7889	0.9177	0.036*
O7	0.58610 (16)	0.65866 (6)	0.56406 (8)	0.0401 (3)
O6	0.21260 (16)	0.86312 (6)	0.75532 (11)	0.0468 (3)
C3	0.27609 (18)	0.68619 (7)	0.24224 (10)	0.0270 (2)
H3	0.2112	0.6542	0.2089	0.032*
C1	0.21182 (18)	0.64213 (6)	0.42338 (11)	0.0277 (3)
O4	0.62267 (16)	0.87514 (5)	0.36029 (9)	0.0413 (3)
C5	0.45307 (18)	0.77855 (7)	0.23509 (10)	0.0276 (3)
H5	0.5090	0.8091	0.1969	0.033*
C7	0.56691 (17)	0.82794 (7)	0.40915 (11)	0.0269 (2)
C4	0.35429 (19)	0.73235 (7)	0.18424 (11)	0.0296 (3)
H4	0.3405	0.7323	0.1112	0.036*
C11	0.48516 (19)	0.70947 (9)	0.91474 (11)	0.0353 (3)
H11	0.5004	0.7044	0.9872	0.042*
C12	0.55921 (18)	0.66641 (8)	0.84784 (11)	0.0312 (3)
H12	0.6234	0.6321	0.8745	0.037*
C8	0.27279 (17)	0.81864 (7)	0.70493 (12)	0.0290 (3)
Cu2	0.0000	0.5000	0.5000	0.03467 (7)
O8	0.70149 (17)	0.59043 (6)	0.68212 (10)	0.0447 (3)
C14	0.61377 (19)	0.63770 (7)	0.65613 (12)	0.0297 (3)
N4	0.06892 (19)	0.55367 (6)	0.62685 (10)	0.0333 (3)
N3	0.2066 (2)	0.45052 (7)	0.53830 (13)	0.0394 (3)
O10	0.2610 (2)	0.52256 (7)	0.21358 (10)	0.0516 (3)
C15	0.3169 (2)	0.49316 (9)	0.60259 (14)	0.0394 (3)
H15A	0.3641	0.5262	0.5591	0.047*
H15B	0.4054	0.4681	0.6370	0.047*
C16	0.2137 (3)	0.52425 (9)	0.68297 (13)	0.0442 (4)
H16A	0.1795	0.4917	0.7324	0.053*
H16B	0.2767	0.5574	0.7218	0.053*
N5	0.28169 (16)	1.02440 (7)	0.51530 (11)	0.0352 (3)
H5A	0.1986	1.0039	0.5433	0.053*
H5B	0.2551	1.0331	0.4479	0.053*
H5C	0.3024	1.0615	0.5498	0.053*
O9	0.0509 (2)	0.94330 (9)	0.60524 (16)	0.0669 (5)
C17	0.4283 (2)	0.98283 (8)	0.52329 (15)	0.0388 (3)
H17A	0.4057	0.9423	0.4860	0.047*
H17B	0.4562	0.9726	0.5966	0.047*
H4A	−0.003 (2)	0.5641 (9)	0.6683 (15)	0.033 (5)*
H3A	0.181 (3)	0.4176 (11)	0.5774 (18)	0.049 (6)*
H4B	0.098 (3)	0.5904 (10)	0.6056 (18)	0.050 (6)*
H3B	0.249 (3)	0.4324 (11)	0.491 (2)	0.054 (6)*
H10A	0.273 (3)	0.4821 (7)	0.2364 (17)	0.055 (6)*
H10B	0.228 (3)	0.5469 (10)	0.2693 (18)	0.079 (8)*
H9A	−0.027 (3)	0.9446 (15)	0.645 (2)	0.082 (10)*
H9B	0.095 (4)	0.9106 (12)	0.640 (2)	0.099 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03397 (10)	0.02360 (8)	0.01879 (7)	0.00059 (6)	0.00018 (6)	0.00041 (6)
N1	0.0263 (5)	0.0217 (4)	0.0186 (4)	−0.0015 (4)	0.0007 (4)	0.0018 (4)
O5	0.0444 (6)	0.0339 (5)	0.0293 (5)	0.0062 (5)	−0.0055 (4)	0.0029 (4)
O3	0.0466 (6)	0.0369 (5)	0.0262 (5)	−0.0096 (5)	−0.0049 (4)	0.0008 (4)
N2	0.0255 (5)	0.0208 (4)	0.0200 (4)	0.0013 (4)	0.0007 (4)	−0.0013 (4)
C2	0.0280 (6)	0.0219 (5)	0.0209 (5)	−0.0012 (4)	0.0006 (4)	−0.0001 (4)
C6	0.0249 (6)	0.0219 (5)	0.0232 (5)	−0.0001 (4)	0.0017 (4)	0.0024 (4)
C9	0.0227 (5)	0.0232 (5)	0.0228 (5)	0.0000 (4)	0.0015 (4)	−0.0028 (4)
O1	0.0582 (7)	0.0317 (5)	0.0227 (4)	−0.0143 (5)	0.0058 (5)	0.0006 (4)
O2	0.0550 (7)	0.0317 (5)	0.0341 (6)	−0.0186 (5)	0.0084 (5)	−0.0054 (4)
C13	0.0267 (6)	0.0227 (5)	0.0230 (5)	0.0017 (5)	0.0038 (5)	0.0012 (4)
C10	0.0312 (7)	0.0365 (7)	0.0233 (6)	0.0025 (6)	0.0040 (5)	−0.0056 (5)
O7	0.0601 (8)	0.0373 (6)	0.0235 (5)	0.0146 (5)	0.0066 (5)	−0.0020 (4)
O6	0.0555 (7)	0.0349 (6)	0.0494 (7)	0.0197 (5)	−0.0035 (6)	−0.0106 (5)
C3	0.0325 (7)	0.0269 (6)	0.0214 (5)	−0.0002 (5)	−0.0006 (5)	−0.0038 (5)
C1	0.0349 (7)	0.0232 (5)	0.0251 (6)	−0.0056 (5)	0.0029 (5)	0.0002 (5)
O4	0.0551 (7)	0.0306 (5)	0.0385 (6)	−0.0163 (5)	0.0059 (5)	0.0026 (5)
C5	0.0321 (7)	0.0289 (6)	0.0221 (5)	0.0011 (5)	0.0042 (5)	0.0061 (5)
C7	0.0276 (6)	0.0241 (5)	0.0290 (6)	−0.0013 (5)	0.0018 (5)	0.0007 (5)
C4	0.0358 (7)	0.0349 (7)	0.0181 (5)	0.0043 (6)	0.0024 (5)	0.0000 (5)
C11	0.0363 (8)	0.0512 (9)	0.0185 (5)	0.0044 (7)	0.0014 (5)	0.0025 (6)
C12	0.0319 (7)	0.0354 (7)	0.0264 (6)	0.0074 (6)	0.0021 (5)	0.0077 (5)
C8	0.0278 (6)	0.0244 (6)	0.0342 (7)	0.0022 (5)	−0.0038 (5)	−0.0017 (5)
Cu2	0.03599 (14)	0.03264 (13)	0.03617 (14)	0.00045 (10)	0.00872 (11)	−0.01548 (11)
O8	0.0584 (8)	0.0315 (5)	0.0455 (7)	0.0218 (5)	0.0139 (6)	0.0061 (5)
C14	0.0377 (7)	0.0231 (5)	0.0287 (6)	0.0051 (5)	0.0064 (5)	−0.0012 (5)
N4	0.0461 (7)	0.0260 (5)	0.0292 (6)	−0.0023 (5)	0.0151 (5)	−0.0052 (5)
N3	0.0467 (8)	0.0333 (7)	0.0395 (7)	0.0063 (6)	0.0122 (6)	−0.0102 (6)
O10	0.0888 (11)	0.0350 (6)	0.0313 (6)	0.0095 (7)	0.0053 (6)	0.0035 (5)
C15	0.0423 (9)	0.0407 (8)	0.0352 (8)	0.0023 (7)	0.0036 (7)	−0.0012 (7)
C16	0.0643 (12)	0.0405 (8)	0.0279 (7)	0.0044 (8)	0.0033 (7)	−0.0041 (6)
N5	0.0316 (6)	0.0360 (6)	0.0377 (7)	−0.0032 (5)	−0.0007 (5)	−0.0016 (5)
O9	0.0400 (7)	0.0670 (10)	0.0921 (12)	−0.0022 (7)	−0.0090 (8)	0.0472 (9)
C17	0.0366 (8)	0.0355 (7)	0.0447 (9)	−0.0001 (6)	0.0070 (7)	0.0026 (7)

Geometric parameters (Å, º) top

Cu1—N2	1.9228 (11)	C4—H4	0.9300
Cu1—N1	1.9549 (11)	C11—C12	1.391 (2)
Cu1—O7	2.1030 (11)	C11—H11	0.9300
Cu1—O5	2.1328 (11)	C12—H12	0.9300
Cu1—O1	2.2808 (11)	Cu2—N3ⁱ	2.0019 (16)
Cu1—O3	2.3041 (11)	Cu2—N3	2.0019 (16)
N1—C6	1.3375 (16)	Cu2—N4	2.0080 (13)
N1—C2	1.3390 (17)	Cu2—N4ⁱ	2.0080 (13)
O5—C8	1.2626 (18)	O8—C14	1.2389 (17)
O3—C7	1.2461 (18)	N4—C16	1.473 (2)
N2—C9	1.3271 (16)	N4—H4A	0.843 (19)
N2—C13	1.3303 (16)	N4—H4B	0.84 (2)
C2—C3	1.3837 (18)	N3—C15	1.469 (2)
C2—C1	1.5188 (18)	N3—H3A	0.87 (2)
C6—C5	1.3834 (18)	N3—H3B	0.80 (2)
C6—C7	1.5146 (19)	O10—H10A	0.883 (15)
C9—C10	1.3826 (19)	O10—H10B	0.921 (16)
C9—C8	1.5162 (19)	C15—C16	1.505 (2)
O1—C1	1.2553 (17)	C15—H15A	0.9700
O2—C1	1.2439 (17)	C15—H15B	0.9700
C13—C12	1.3772 (19)	C16—H16A	0.9700
C13—C14	1.5109 (18)	C16—H16B	0.9700
C10—C11	1.384 (2)	N5—C17	1.467 (2)
C10—H10	0.9300	N5—H5A	0.8900
O7—C14	1.2567 (18)	N5—H5B	0.8900
O6—C8	1.2350 (18)	N5—H5C	0.8900
C3—C4	1.381 (2)	O9—H9A	0.831 (17)
C3—H3	0.9300	O9—H9B	0.875 (17)
O4—C7	1.2520 (17)	C17—C17ⁱⁱ	1.516 (3)
C5—C4	1.380 (2)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700

N2—Cu1—N1	173.52 (4)	C10—C11—H11	119.9
N2—Cu1—O7	79.31 (4)	C12—C11—H11	119.9
N1—Cu1—O7	95.33 (4)	C13—C12—C11	118.20 (13)
N2—Cu1—O5	78.49 (4)	C13—C12—H12	120.9
N1—Cu1—O5	107.04 (4)	C11—C12—H12	120.9
O7—Cu1—O5	157.55 (4)	O6—C8—O5	126.80 (14)
N2—Cu1—O1	99.47 (4)	O6—C8—C9	118.08 (13)
N1—Cu1—O1	76.64 (4)	O5—C8—C9	115.12 (12)
O7—Cu1—O1	88.96 (5)	N3ⁱ—Cu2—N3	180.0
O5—Cu1—O1	97.89 (5)	N3ⁱ—Cu2—N4	96.20 (6)
N2—Cu1—O3	107.65 (4)	N3—Cu2—N4	83.80 (6)
N1—Cu1—O3	76.64 (4)	N3ⁱ—Cu2—N4ⁱ	83.80 (6)
O7—Cu1—O3	99.06 (5)	N3—Cu2—N4ⁱ	96.20 (6)
O5—Cu1—O3	84.60 (5)	N4—Cu2—N4ⁱ	180.00 (6)
O1—Cu1—O3	152.68 (4)	O8—C14—O7	125.87 (13)
C6—N1—C2	120.58 (11)	O8—C14—C13	118.69 (13)
C6—N1—Cu1	120.18 (9)	O7—C14—C13	115.42 (12)
C2—N1—Cu1	119.20 (8)	C16—N4—Cu2	110.04 (10)
C8—O5—Cu1	113.42 (9)	C16—N4—H4A	111.8 (13)
C7—O3—Cu1	110.25 (9)	Cu2—N4—H4A	118.2 (13)
C9—N2—C13	122.16 (11)	C16—N4—H4B	106.9 (15)
C9—N2—Cu1	119.64 (9)	Cu2—N4—H4B	107.7 (16)
C13—N2—Cu1	118.20 (8)	H4A—N4—H4B	101.2 (19)
N1—C2—C3	121.04 (12)	C15—N3—Cu2	108.13 (10)
N1—C2—C1	115.09 (11)	C15—N3—H3A	107.5 (15)
C3—C2—C1	123.82 (12)	Cu2—N3—H3A	108.0 (14)
N1—C6—C5	121.00 (12)	C15—N3—H3B	114.6 (17)
N1—C6—C7	114.86 (11)	Cu2—N3—H3B	116.4 (17)
C5—C6—C7	124.12 (12)	H3A—N3—H3B	101 (2)
N2—C9—C10	120.42 (12)	H10A—O10—H10B	106.7 (17)
N2—C9—C8	112.77 (11)	N3—C15—C16	106.47 (15)
C10—C9—C8	126.78 (12)	N3—C15—H15A	110.4
C1—O1—Cu1	110.04 (9)	C16—C15—H15A	110.4
N2—C13—C12	120.68 (12)	N3—C15—H15B	110.4
N2—C13—C14	113.03 (11)	C16—C15—H15B	110.4
C12—C13—C14	126.20 (12)	H15A—C15—H15B	108.6
C9—C10—C11	118.42 (12)	N4—C16—C15	107.96 (13)
C9—C10—H10	120.8	N4—C16—H16A	110.1
C11—C10—H10	120.8	C15—C16—H16A	110.1
C14—O7—Cu1	113.50 (9)	N4—C16—H16B	110.1
C4—C3—C2	118.76 (13)	C15—C16—H16B	110.1
C4—C3—H3	120.6	H16A—C16—H16B	108.4
C2—C3—H3	120.6	C17—N5—H5A	109.5
O2—C1—O1	126.87 (13)	C17—N5—H5B	109.5
O2—C1—C2	117.84 (12)	H5A—N5—H5B	109.5
O1—C1—C2	115.30 (11)	C17—N5—H5C	109.5
C4—C5—C6	118.86 (12)	H5A—N5—H5C	109.5
C4—C5—H5	120.6	H5B—N5—H5C	109.5
C6—C5—H5	120.6	H9A—O9—H9B	91 (3)
O3—C7—O4	126.50 (14)	N5—C17—C17ⁱⁱ	110.25 (17)
O3—C7—C6	117.18 (12)	N5—C17—H17A	109.6
O4—C7—C6	116.32 (13)	C17ⁱⁱ—C17—H17A	109.6
C5—C4—C3	119.72 (12)	N5—C17—H17B	109.6
C5—C4—H4	120.1	C17ⁱⁱ—C17—H17B	109.6
C3—C4—H4	120.1	H17A—C17—H17B	108.1
C10—C11—C12	120.11 (13)

O7—Cu1—N1—C6	−100.17 (11)	C8—C9—C10—C11	−178.36 (14)
O5—Cu1—N1—C6	77.88 (11)	N2—Cu1—O7—C14	6.88 (11)
O1—Cu1—N1—C6	172.17 (11)	N1—Cu1—O7—C14	−169.43 (11)
O3—Cu1—N1—C6	−2.10 (10)	O5—Cu1—O7—C14	15.4 (2)
O7—Cu1—N1—C2	77.69 (10)	O1—Cu1—O7—C14	−92.96 (12)
O5—Cu1—N1—C2	−104.25 (10)	O3—Cu1—O7—C14	113.29 (12)
O1—Cu1—N1—C2	−9.96 (10)	N1—C2—C3—C4	0.3 (2)
O3—Cu1—N1—C2	175.77 (11)	C1—C2—C3—C4	177.64 (13)
N2—Cu1—O5—C8	6.16 (10)	Cu1—O1—C1—O2	160.26 (14)
N1—Cu1—O5—C8	−177.35 (10)	Cu1—O1—C1—C2	−20.20 (16)
O7—Cu1—O5—C8	−2.43 (19)	N1—C2—C1—O2	−166.87 (13)
O1—Cu1—O5—C8	104.28 (11)	C3—C2—C1—O2	15.7 (2)
O3—Cu1—O5—C8	−103.11 (11)	N1—C2—C1—O1	13.55 (19)
N2—Cu1—O3—C7	−177.91 (10)	C3—C2—C1—O1	−163.89 (14)
N1—Cu1—O3—C7	7.14 (10)	N1—C6—C5—C4	0.6 (2)
O7—Cu1—O3—C7	100.50 (10)	C7—C6—C5—C4	−177.81 (13)
O5—Cu1—O3—C7	−101.83 (10)	Cu1—O3—C7—O4	169.07 (13)
O1—Cu1—O3—C7	−5.07 (16)	Cu1—O3—C7—C6	−10.36 (15)
O7—Cu1—N2—C9	174.33 (11)	N1—C6—C7—O3	9.37 (19)
O5—Cu1—N2—C9	−2.34 (10)	C5—C6—C7—O3	−172.16 (14)
O1—Cu1—N2—C9	−98.55 (10)	N1—C6—C7—O4	−170.12 (13)
O3—Cu1—N2—C9	78.13 (11)	C5—C6—C7—O4	8.4 (2)
O7—Cu1—N2—C13	−5.37 (10)	C6—C5—C4—C3	−1.9 (2)
O5—Cu1—N2—C13	177.95 (11)	C2—C3—C4—C5	1.5 (2)
O1—Cu1—N2—C13	81.74 (10)	C9—C10—C11—C12	−0.2 (2)
O3—Cu1—N2—C13	−101.58 (10)	N2—C13—C12—C11	−0.7 (2)
C6—N1—C2—C3	−1.7 (2)	C14—C13—C12—C11	175.45 (14)
Cu1—N1—C2—C3	−179.57 (10)	C10—C11—C12—C13	0.6 (2)
C6—N1—C2—C1	−179.23 (12)	Cu1—O5—C8—O6	171.92 (14)
Cu1—N1—C2—C1	2.91 (15)	Cu1—O5—C8—C9	−8.36 (16)
C2—N1—C6—C5	1.2 (2)	N2—C9—C8—O6	−173.61 (13)
Cu1—N1—C6—C5	179.08 (10)	C10—C9—C8—O6	4.7 (2)
C2—N1—C6—C7	179.77 (11)	N2—C9—C8—O5	6.65 (18)
Cu1—N1—C6—C7	−2.39 (15)	C10—C9—C8—O5	−175.07 (14)
C13—N2—C9—C10	0.1 (2)	Cu1—O7—C14—O8	174.91 (13)
Cu1—N2—C9—C10	−179.56 (10)	Cu1—O7—C14—C13	−6.97 (17)
C13—N2—C9—C8	178.54 (11)	N2—C13—C14—O8	−178.92 (13)
Cu1—N2—C9—C8	−1.15 (15)	C12—C13—C14—O8	4.7 (2)
N2—Cu1—O1—C1	−157.62 (10)	N2—C13—C14—O7	2.82 (19)
N1—Cu1—O1—C1	17.09 (10)	C12—C13—C14—O7	−173.59 (15)
O7—Cu1—O1—C1	−78.64 (11)	N3ⁱ—Cu2—N4—C16	173.36 (12)
O5—Cu1—O1—C1	122.82 (10)	N3—Cu2—N4—C16	−6.64 (12)
O3—Cu1—O1—C1	29.29 (16)	N4—Cu2—N3—C15	−22.24 (11)
C9—N2—C13—C12	0.3 (2)	N4ⁱ—Cu2—N3—C15	157.76 (11)
Cu1—N2—C13—C12	−179.98 (11)	Cu2—N3—C15—C16	45.93 (16)
C9—N2—C13—C14	−176.31 (12)	Cu2—N4—C16—C15	33.54 (17)
Cu1—N2—C13—C14	3.39 (15)	N3—C15—C16—N4	−52.17 (18)
N2—C9—C10—C11	−0.2 (2)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1	0.84 (2)	2.07 (2)	2.8697 (17)	160 (2)
O10—H10B···O2	0.92 (2)	1.87 (2)	2.7927 (17)	176 (3)
N5—H5A···O9	0.89	1.93	2.808 (2)	167
O9—H9B···O5	0.88 (2)	2.50 (2)	3.211 (2)	139 (3)
O9—H9B···O6	0.88 (2)	1.96 (2)	2.793 (2)	159 (3)
N3—H3A···O6ⁱⁱⁱ	0.87 (2)	2.51 (2)	3.218 (2)	138.5 (18)
O9—H9A···O10^iv	0.83 (2)	2.10 (2)	2.893 (3)	160 (3)
N5—H5B···O9^v	0.89	2.59	3.106 (2)	118
N5—H5B···O10^vi	0.89	2.06	2.9151 (19)	160
N5—H5C···O4ⁱⁱ	0.89	1.82	2.6882 (18)	166
N4—H4A···O8^vii	0.843 (19)	2.482 (19)	3.2079 (19)	144.8 (17)
O10—H10A···O8^viii	0.88 (2)	1.82 (2)	2.6824 (17)	165 (2)
N3—H3B···O8^viii	0.80 (2)	2.31 (3)	3.0664 (19)	156 (2)
N3—H3B···O7^viii	0.80 (2)	2.43 (2)	3.1383 (17)	147 (2)

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x, −y+2, −z+1; (vi) −x+1/2, y+1/2, −z+1/2; (vii) x−1, y, z; (viii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₃(C₇H₃NO₄)₄(C₂H₈N₂)₂]·C₂H₈N₂·4H₂O
M_r	1105.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.152 (2), 20.538 (5), 12.736 (3)
β (°)	93.44 (2)
V (Å³)	2128.5 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.51 × 0.28 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.583, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	35349, 9453, 6734
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.810

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 1.02
No. of reflections	9453
No. of parameters	336
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.47

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1	0.84 (2)	2.07 (2)	2.8697 (17)	160 (2)
O10—H10B···O2	0.921 (16)	1.874 (16)	2.7927 (17)	176 (3)
N5—H5A···O9	0.89	1.93	2.808 (2)	167.4
O9—H9B···O5	0.875 (17)	2.50 (2)	3.211 (2)	139 (3)
O9—H9B···O6	0.875 (17)	1.96 (2)	2.793 (2)	159 (3)
N3—H3A···O6ⁱ	0.87 (2)	2.51 (2)	3.218 (2)	138.5 (18)
O9—H9A···O10ⁱⁱ	0.831 (17)	2.10 (2)	2.893 (3)	160 (3)
N5—H5B···O9ⁱⁱⁱ	0.89	2.59	3.106 (2)	117.7
N5—H5B···O10^iv	0.89	2.06	2.9151 (19)	159.5
N5—H5C···O4^v	0.89	1.82	2.6882 (18)	166.3
N4—H4A···O8^vi	0.843 (19)	2.482 (19)	3.2079 (19)	144.8 (17)
O10—H10A···O8^vii	0.883 (15)	1.821 (16)	2.6824 (17)	165 (2)
N3—H3B···O8^vii	0.80 (2)	2.31 (3)	3.0664 (19)	156 (2)
N3—H3B···O7^vii	0.80 (2)	2.43 (2)	3.1383 (17)	147 (2)

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x, −y+2, −z+1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+2, −z+1; (vi) x−1, y, z; (vii) −x+1, −y+1, −z+1.

Acknowledgements

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.

References

Aghabozorg, H., Ghasemikhah, P., Ghadermazi, M., Attar Gharamaleki, J. & Sheshmani, S. (2006). Acta Cryst. E62 2269–2271. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Douki, T., Setlow, B. & Setlow, P. (2005). J. Photochem. Photobiol. B, 4, 591–597. CrossRef CAS Google Scholar
Kazuhiro, Y., Noriko, Y. & Tadayasu, F. (1994). Eur. Patent No. EP0603165. Google Scholar
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Park, H., Lough, A. J., Kim, J. C., Jeong, M. H. & Kang, Y. S. (2007). Inorg. Chim. Acta, 360 2819–2823. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, J. R. H., Smitth, V. H. Jr & Allen, R. E. (2006). Chem. Phys. 322 254–268. Web of Science CrossRef CAS Google Scholar

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Volume 68| Part 6| June 2012| Pages m830-m831

doi:10.1107/S1600536812022039

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

[(Pyridine-2,6-di­carboxyl­ato)copper(II)]-μ-(pyridine-2,6-di­carboxyl­ato)-[bis­­(ethyl­enedi­amine)­copper(II)]-μ-(pyridine-2,6-di­carboxyl­ato)-[(pyridine-2,6-di­carboxyl­ato)copper(II)] ethyl­enedi­amine monosolvate tetra­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

[(Pyridine-2,6-dicarboxylato)copper(II)]-μ-(pyridine-2,6-dicarboxylato)-[bis(ethylenediamine)copper(II)]-μ-(pyridine-2,6-dicarboxylato)-[(pyridine-2,6-dicarboxylato)copper(II)] ethylenediamine monosolvate tetrahydrate